CN86100906A - Reduce RS Regenerator Section method of temperature in the fluid catalytic cracking process - Google Patents

Reduce RS Regenerator Section method of temperature in the fluid catalytic cracking process Download PDF

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CN86100906A
CN86100906A CN86100906.1A CN86100906A CN86100906A CN 86100906 A CN86100906 A CN 86100906A CN 86100906 A CN86100906 A CN 86100906A CN 86100906 A CN86100906 A CN 86100906A
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catalyzer
temperature
low
solid particulate
regenerator section
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CN1004141B (en
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罗伯特·A·伦治曼
格雷戈里·J·汤普森
安东尼·G·维克斯
雷蒙德·W·莫特
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Honeywell UOP LLC
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides

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  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
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Abstract

The fluid catalytic cracking process that the present invention relates to handle high carboloy residue hydrocarbons raw oil (recovered temperature of its 50% (volume) fraction is higher than 500) reduces the working method of RS Regenerator Section temperature.This method mainly comprises: but stock oil is contacted with fluidizing regeneration cracking catalyst and low non-catalytic coke solid particle at conversion zone, hydrocarbon product is separated with it, reclaim hydrocarbon product, catalyzer and low coke solid particle are delivered to the regeneration of RS Regenerator Section decoking, then it are delivered to conversion zone and contact with stock oil.Compare with the same operating gear that does not add low coke solid particle, present method can make RS Regenerator Section keep lesser temps, does not reduce the carbon-burning capacity of RS Regenerator Section again, does not also influence the operation of conversion zone.

Description

Reduce RS Regenerator Section method of temperature in the fluid catalytic cracking process
Technical scope under the present invention is when handling high coking property (high-coke-make) raw material with fluid catalytic cracking process the temperature of RS Regenerator Section to be minimized.Or rather, the present invention relates to a kind of method that reduces the top temperature that RS Regenerator Section reached in the fluid catalytic cracking process under the situation that does not reduce amount of burnt.But used way is to allow the low coking property solid particulate of fluidizing mix circulation simultaneously with cracking catalyst.This low coking property particulate surface-area is at about 5 meters 2Below/the gram, and according to the ASTM(ASTM (American society for testing materials)) standard only produces coke below about 0.2% weight with the method (hereinafter to be referred as the ASTM-MAT method) of little activity test (MAT) calibrating fluidisation catalyst for cracking performance when testing.The low coking property particulate of this kind consumption should satisfy that to make it and the ratio of cracking catalyst be about 1: 100 to about 10: 1.Can make the breeding blanket temperature reduce about 10 °F to about 250 °F (6 ℃ to 139 ℃) in view of the above, and to the operation of conversion zone and have no adverse effect.
In No. 2889269 and No. 2894902 United States Patent (USP), but Buddhist nun's Ademilson (Nicholson) has proposed certain methods.But wherein, in fluidized reactor-regenerator system, circulate, to reach the purpose of from revivifier, heat being taken away with regard to useful levigated catalyzer and fluidizing inertia thermofor particle.But these methods are mainly used in the fluidisation hydroforming process of petroleum naphtha, and do not use the raw material of high coking property, do not touch yet do not influence that reactor is partly operated and revivifier part carbon-burning capacity situation under reduce the problem of regenerator temperature.Above-mentioned two patents had not both been announced the problem of also unresolved the present invention's statement, did not use surface-area less than about 5 meters in fluid catalytic cracking process yet 2/ gram and when measuring by the ASTM-MAT method coking amount be lower than about 0.2%(weight) but the fluidizing low coke solid particle.If adopt this particle just can make RS Regenerator Section keep lesser temps and not influence the carbon-burning capacity of RS Regenerator Section or the operation of conversion zone.
In No. 4289605 United States Patent (USP), Ba Suolike (Bartholic) has announced a kind of fluid catalytic cracking process, and its method is that metallic hydrocarbon feed is contacted with the mixture of active cracking catalyst and porous inert solid particle.The feature of porous inert particle is made up of the hole of diameter more than 100 dusts preferably, and its hole volume is no less than 50%, and the surface-area of every gram material should be about 10 to about 15 square metres.A kind of preferably porous inert solid particle is burnt kaolinton.Adopting the main purpose of macropore inert solid is the macromole of accepting to contain metal in the charging selectively and producing the Kang Laxun carbon residue.This patent both not mentioned when adopting high coking property raw material to RS Regenerator Section temperature controlling and problem that reactor is partly operated and had no adverse effect, do not point out that its key is to use such class to hang down the coking property solid particulate yet, the latter's characteristics are to have about 5 meters 2The surface-area that/gram is following also only produces 0.2%(weight when check by the ASTM-MAT method) below coke.These particulate add, and just a certain amount of catalyzer are played a kind of adjection and can not replace catalyzer, and these catalyzer add for reaching the desired target in reactor aspect.
In 2116062A and two parts of UK Patent Application of 2116202A, Olympic Competition row people such as (Occelli) disclose in catalytic cracking be the mixture of solid cracking catalyst and thinner, thinner is the mixture that contains selected aluminum oxide or it and one or more made of heat resistant inorganic compounds.The surface-area of such salic thinner is 30 to 1000 meters 2/ gram, the hole volume is 0.05 to 2.5 centimetre 3/ gram.Even using the purpose of the big thinner of surface-area is that catalyst system still can normally be used when metal content is very high on its surface.These two parts of applications had not both related to the temperature control in the revivifier, and the circulation of also not mentioned low coking property solid particulate and this particulate specific surface are less than about 5 meters 2/ gram only produces the coke below about 0.2% weight when checking by the ASTM-MAT method.This kind particle can be used for reducing the RS Regenerator Section temperature and unlikely conversion zone operation is had a negative impact.
Previous heat extraction method commonly used is that the coiled pipe that is full of refrigerant is installed in revivifier, and it is contacted with the catalyzer for the treatment of decoking.For example, No. 3990992 United States Patent (USP) of Mei Delin people's such as (Medlin) No. 2819951 United States Patent (USP), Mai Kaini (Mckinney) and No. 4219442 United States Patent (USP) of Wei Kansi (Vickers) have all been announced a kind of fluid catalytic cracking process of two section revivifiers, second section of two sections revivifiers cooling coil are housed.These cooling coils must always be full of refrigerant, and constantly from revivifier heat are taken away, even also be like this when start-up least wishes heat taken away.This is because of the metallurgical principles according to classics, without refrigerant it is kept cooling relatively as (reaching as high as 1350 °F (732 ℃)) under the high temperature that coiled pipe is exposed to revivifier, and coiled pipe must be damaged.And cooling coil must reduce the temperature that turns back to the catalyzer of regenerated that goes in the reactor after the circulation.Therefore, remain unchanged in order to make temperature of reactor, must additionally increase some catalyzer and participate in circulation, the result will produce more coke, thereby further reduce the yield of valuable product liquid.
One of one embodiment of the invention narration is by RS Regenerator Section and the conversion zone working method that is used for handling the fluidized catalytic cracker of high coking property hydrocarbon raw material dimerous.The 50%(volume is arranged in this raw material approximately) the fraction temperature be higher than about 500 °F (260 ℃).This working method is included under the coking conversion condition of heat absorption, raw material is contacted with the mixture of being made up of cracking catalyst of regenerating and the non-catalytic refractory inorganic oxide solid particulate of low coking that is in fluidized state and heated at conversion zone, and this mixture is to form in about 1: 100 to about 10: 1 by the ratio of low coking property solid particulate and cracking catalyst.This low coking property solid particulate should have about 5 meters 2/ gram following table area and only produce about 0.2%(weight when check by the ASTM-MAT method) below coke; Separating obtained hydrocarbon product from the mixture of decaying catalyst and low coking property solid particulate; Reclaim the hydrocarbon product of gained; To be sent to RS Regenerator Section by the mixture that cracking catalyst and low coking property solid particulate are formed so that reheat and make it regeneration with the heat release of coke burning; The mixture of cracking catalyst that will heat and regenerate and low coking property solid particulate then, being sent to conversion zone from RS Regenerator Section contacts with raw material, RS Regenerator Section is maintained than same operation and during with low coking property solid particulate on the lower temperature, and not reduce the RS Regenerator Section carbon-burning capacity or operation has a negative impact to conversion zone.
It is used because of the 50%(volume is arranged in former at it that another embodiment of the invention has been narrated the catalyzer cracking method that a high coking property hydro carbons of usefulness makes raw material) more than the fraction temperature be higher than about 500 °F (260 ℃).The granular solids cracking catalyst that this method allows raw material heat with round-robin under the heat release cracking conditions contacts, component in the raw material can be converted into low boiling point hydrocarbon at conversion zone thus, and with catalyzer following current cooling, and actively low contain the charcoal pollutant sediment thereon.Can make its catalytic cracking activity of contaminated catalyst regeneration by burning sedimentary carbonaceous.These carry out in RS Regenerator Section under the heat release condition, and the result makes this catalyzer and RS Regenerator Section all reach certain unacceptable or undesirable top temperature.The catalyzer of regenerating like this is recycled to conversion zone from RS Regenerator Section, but and circulates simultaneously by low coking property refractory inorganic oxide solid particulate of fluidizing and cracking catalyst are mixed and can reduce the top temperature that RS Regenerator Section reaches and do not reduce its amount of burnt.The low coking property solid particles surface of this kind is amassed at about 5 meters 2Below/the gram, and only produce about 0.2%(weight when checking by the ASTM-MAT method) following coke, the used amount of this solid particulate should satisfy that to make it and the ratio of cracking catalyst be about 1: 100 to about 10: 1.In view of the above, the breeding blanket temperature is descended about 10 °F to about 250 °F (6 to 139 ℃) and conversion zone operation is not had detrimentally affect.
Other embodiments of the present invention have comprised further details, such as charging explanation, catalyzer and low coking property solid property and operational condition, announce successively when all these are discussed below each details of the present invention.
Accompanying drawing has been described an embodiment preferably of the present invention, and it is the equipment front view that share that proposes according to basic invention.Other type equipment may also be fit to the present invention's usefulness.
Mainly be converted into lighter and more value product than heavy oil kind raw material such as vacuum gas oil and other so far by fluid catalytic cracking process (hereinafter to be referred as FCC).FCC relates to raw material (no matter being vacuum gas oil or another kind of oil) and contacts with the solid catalysis material of levigated or pulverizing in conversion zone, proterties is the same with fluid after these materials and gas or the vapor mixing, and have the ability of catalytic cracking reaction, and the cracking reaction by-product coke is deposited on their surface in this process.Coke is made up of as materials such as sulphur hydrogen, carbon and other, and it can influence the catalytic activity of FCC catalyzer.With the equipment that coke is removed from the FCC catalyzer, promptly so-called reclaim equiment or revivifier, they are included within the FCC apparatus usually.Revivifier makes the catalyzer that polluted by coke and oxygen-containing gas contact making the coke oxidation and discharge under the condition of significant heat.The stack gas that the gaseous product of wherein a part of heat after by excessive regeneration gas and coke oxidation formed is taken away from revivifier, remaining heat with regenerate or relatively nothing Jiao's catalyzer leave revivifier.The revivifier that pressurization is operated down is usually by having adorned the turbine that recovered energy is used, volumetric expansion when it overflows stack gas from revivifier, thereby this part energy that discharges in the recovery expansion process.
Fluidisation catalyzer between conversion zone and RS Regenerator Section constantly the circulation.This fluidized catalyst can also play carrier function except playing katalysis, and heat is sent to another section from a section.The catalyzer that leaves conversion zone is called as " decaying catalyst ", that is to say, this catalyzer is because of the top partly inactivation of coke that deposited.The catalyzer of having disposed coke is called as " regenerated catalyst ".
Conversion of raw material is controlled by attemperation, catalyst activity and catalytic amount (that is ratio of catalyzer and oil) in the conversion zone.The most common way of attemperation is the cycle rate of the catalyzer that goes in regulating from the RS Regenerator Section to the conversion zone, and doing has so also increased simultaneously the ratio of catalyzer to oil.That is to say that if want to increase transformation efficiency, the catalyst circulation rate that increases from the revivifier to the reactor is effective.Because under normal operating condition, the temperature in the RS Regenerator Section can increase the conversion zone temperature more than temperature height in the conversion zone so increase from the catalyzer speed of the colder conversion zone of the hot RS Regenerator Section flow direction.
Recently, because the restrictive policy on the political economy has influenced the oil supplying of trade Central Plains and has made and be necessary to adopt extraordinary heavy oil as raw material in FCC apparatus.Now FCC apparatus must be dealt with such as the such class raw material of residual oil, and may also need use in the future heavy crude and coal or with the mixture of shale derived oils.
The chemical property of the raw material that uses in the FCC apparatus and molecular structure will influence the coking amount on the decaying catalyst.In general, the molecular weight of charging is higher, and the Kang Laxun carbon residue is just higher, and heptane insolubles is also higher, and ratio of carbon-hydrogen is higher, and coking amount is also higher on the decaying catalyst.Equally, fixed nitrogen amount higher (just as what find in the shale oil) also can make coking amount increase on the decaying catalyst.The raw material that processing is more and more heavy, particularly process deasphalted oil or direct processing atmospheric distillation tower bed material from coarse and crude equipment, be common so-called residual oil, can cause that really some factor increases together in the above-mentioned factor, thereby cause that coking amount increases on the decaying catalyst.
The amount of coke increase causes in every pound of recycling catalyst a large amount of coke burnings being arranged in the revivifier on the decaying catalyst.On the one hand by stack gas, main regenerated catalyst fluidisation by heat is taken away heat from revivifier in FCC apparatus commonly used.The amount of coke increase will make temperature increase in the revivifier on the decaying catalyst.Yet the temperature that the FCC catalyzer can stand is limited after all, otherwise can produce substantial disadvantageous effect to catalyst activity.In general, for FCC catalyzer in modern age commonly used, the regeneration temperature of catalyzer maintains below 1400 °F (760 ℃) usually, because temperature surpasses about 1400-1450 °F (760 to 788 ℃), the activity of such catalysts loss will be very serious.
In order to burn more substantial coke in revivifier but also will keep top temperature to be no more than about 1400 °F (760 ℃), prior art is pointed out to be contained in coiled pipe in the revivifier or to make it to link together with revivifier widely.Must fill heat-eliminating medium frequently with the cooling coil that the FCC RS Regenerator Section is supporting, these coiled pipes are counted as the weak link in the whole FCC process.
The objective of the invention is to reduce the temperature of RS Regenerator Section and heat is sent to conversion zone and does not influence the operation of conversion zone or the carbon-burning capacity of restriction RS Regenerator Section from RS Regenerator Section.
We have found that is reduced a RS Regenerator Section method of temperature in the fluid catalytic cracking process, but promptly allow catalyzer and mixture contact, allow catalyzer and low coking property solid particulate both be reproduced and recycle then with hydrocarbon raw material with low coking property solid particulate of fluidisation granularity.
Catalyzer relies on its catalytic cracking activity can be with the raw material cracking, but can produce the coke as the process byproduct in its surface.We find that best bet is that granules of catalyst is circulated with the particle that another kind seldom can produce coke.To be this particle mix the amount of coke of using the back to be produced with granules of catalyst to employed low coking property particulate important criteria is in the amount of coke that generates under this reaction environment separately with these granules of catalyst and compares the coke that does not generate additional quantity in selecting the present invention.Here claim this back one class particle to be low coking property solid particulate.
The invention provides a kind of production method, can make various hydrocarbon ils continuous catalysis be converted into the lower product of molecular weight, and make the higher product liquid output maximum of value by this method.If necessary, also can remove the processing treatment as hydrogenation and so on of underpressure distillation and other costliness from, the raw material that suitable the present invention uses comprises residual hydrocarbon ils or any other hydrocarbon raw material, and wherein the fraction temperature is higher than half of accounted for cumulative volume of about 500 (260 ℃).So-called " residual hydrocarbon ils " not only comprise under the room temperature for liquid those mainly belong to the component of hydro carbons, and comprise under the normal temperature be pitch or tar but be heated to about 800 °F (427 ℃) or can liquefy during higher temperature those mainly belong to the component of hydro carbons.The raw material that suitable the present invention uses is a residual oil, no matter whether it derives from oil.For example, the present invention can be used to process some raw materials that have nothing in common with each other like this, as the heavy that gets from crude oil low oil, heavy bitumen crude oil, be called those crude oil of " heavy crude ", the aromatic series extract when its character approaches the extract of gained behind the reduced oil, solvent deasphalting of Residual oil, shale oil, tar sand extract (tar sand ext-ract), gelatin liquefaction product and solvation coal product, normal pressure and decompression and bed material, lubricating oil refining, tar leftover bits and pieces, heavy recycle stock, waste oil, other refinery's waste liquid and composition thereof.These mixtures for example, can comprise that oil, Jiao, pitch and so on thing mixes with the various hydro carbons compositions that are easy to get.Equally, the present invention can be applicable to the raw material of hydrotreatment, but one of advantage of the present invention is that it can successfully transform the Residual oil that does not pass through pre-hydrotreatment.Yet present method more is applicable to the mixture of handling reduced oil or its virgin gas oil.So-called reduced oil is meant the seethe with excitement fraction of gained of crude oil under 650 (343 ℃) or higher temperature.Though do not get rid of the material that underpressure distillation is passed through in use in advance, benefit of the present invention is that it can handle raw material without underpressure distillation satisfactorily, thereby compares with traditional FCC process that needs vacuum distillation apparatus, can save capital investment and process cost.Certainly gas oil and also be the raw material that is suitable for through the gas oil of underpressure distillation.
An important step of the production process that the present invention proposes is between the hydrocarbon raw material transition phase, but the circulation of the low coking property solid particulate of fluidizing.Available low coking property solid particulate preferably includes the fireproof inorganic oxide, for example corundum, mullite, fused alumina, fused silica, Alpha-alumina, low surface area calcined clay and so on.No matter select for use which class to hang down the coking property solid particulate, these particles must show the trend that little increase is in the last coke content of solid (catalyzer adds low coking property solid particulate) under the reaction environment.And, more also be very necessary, promptly the surface-area of this low coke solid particle is at about 5 meters 2/ gram is following and only generate about 0.2%(weight on the solid particulate when press the check of ASTM-MAT method) below coke.If additional solid particulate can generate relatively large extra coke, so just there is additional heat in FCC, to discharge.Revivifier will tend to lose efficacy or be difficult to reach the purpose that reduces regenerator temperature.Similarly, the low surface area feature of low coking property solid particulate make these particles deliver to before the RS Regenerator Section might be in conversion zone not only soon but also fully separate with the reaction product of hydrocarbon-containifirst.Can prevent that with this way these flammable hydro carbons from entering RS Regenerator Section and the release that prevents additional heat.This low coking property solid particulate also must have no adverse effect to hydrocarbon conversion process, and must be the stable physical damage that causes because of heat and mechanical force that can run in process of production of resisting in other words.The variable size of low coking property solid particulate moves between about 5 microns to about 2000 microns, and preferably sphere or ellipsoidal particle.In one embodiment of the invention, the mixture of catalyzer and low coking property solid particulate introduced contacting with hydrocarbon raw material, catalyzer and low coking property particulate size range can be essentially identical, and be intersection or different.The apparent bulk density of the low coking property solid particulate of this kind can change in about 0.3 grams per milliliter between about 4 grams per milliliters.
The low coking property solid of main usefulness is more such materials in production process of the present invention: during promptly with the check of ASTM-MAT method, only produce about 0.2%(weight on its surface) following coke.This little activity test more formally is called the standard method with little activity test calibrating fluidisation catalyst for cracking performance, and is designated as the D3907-80 test.This little activity test is also narrated in No. 4493902 United States Patent (USP) to some extent.Little activity test is to carry out on a laboratory testing rig by above-mentioned standard method design and operation.In brief, the program of this little activity test is as follows: claiming the 4 gram particulate samples reactor of packing into, heavily is the speed of 1.33 grams to inject per 75 seconds then, gas oil is injected the reactor that maintains 900 (482 ℃).This moment, particle was about 3 and the weight-space velocity of Hour is about 16 with the weight ratio of oil.Then the available standards method is determined conversion of raw material and is stayed amount of coke on the useless particle.
Though below discussion and non-exhaustive but can be used to illustrate and utilize the low coking property solid particulate that the present invention proposes and the main benefit that obtains.The circulation of low coking property solid particulate obviously reduces the revivifier service temperature, and fall surpasses need not hang down the index that the coking property solid particulate only makes catalyst recirculation reach.Reducing these characteristics of regenerator temperature is cardinal task for hydrocarbon conversion industry, because much contain the component that a large amount of distillations do not go out in the FCC raw material that generally uses at present, they generate coke, and these coke finally must be removed from the solid particulate that is circulating at regeneration period.To produce the heat of huge amount in the burning of a large amount of charcoals of regeneration period or coke, these heats must shed in some way.Because modern FCC catalyzer is tetchy for high temperature, and high like this temperature is just arranged in high-temp regenerator.This susceptibility to temperature finally can cause catalyst activity and optionally reduce.Therefore, the lower regenerator temperature that realizes by the present invention helps to keep the cracking activity and the selectivity of catalyzer, and also the selection for operational condition provides greater flexibility.The circulation of low coking property solid particulate also reduces in order to keep certain activity needs additional catalytic amount, and catalyzer will keep the longer time to its activity like this.
Fluidised FCC catalyzer is another integral part of the present invention.Usually, recommend to select for use to have remarkable cracking activity, can in the short residence time, obtain the catalyzer of high conversion and productive rate.This catalyzer can be fresh or used form adition process in, for example previous used equilibrium catalyst.People can adopt the arbitrary hydrocarbon cracking catalyzer with above-mentioned characteristic.Those have the catalyzer of vesicular structure type special recommendation.Raw molecule can enter in the hole of porous catalyst, in the hole or the hole near and/or contact with the active catalytic center.Various these class catalyzer comprise the laminar silicic acid salt, and it is effective if you would taking off Shi Dengdou.Though most widely used in this class catalyzer is the famous catalyzer that contains zeolite, the present invention has also done careful consideration to the catalyzer that does not contain zeolite.The catalyzer that contains zeolite can comprise any zeolite, no matter be natural, semi-synthetic or synthetic, single or with other materials that catalyzer is not had obvious damage blended mutually, as long as the catalyzer that generates have above-mentioned activity and a vesicular structure can.For example if catalyzer is a mixture, wherein contained zeolite component can be to combine or be dispersed in wherein with porous refractory inorganic oxide carrier.In this case, the weight percent of this catalyzer can be about 1% to about 60%, and about 1% to about 40% is better, preferably about 5% to about 25%.This percentage ratio is the weight with zeolite catalyst (butt), adds that the porous refractory inorganic oxide catalyst weight that has additive or do not have additive is that radix calculates.This additive is in order to quicken or to suppress various needs or unwanted reaction and add.To the general remark of the useful zeolite catalyst kind of the present invention at " Refi-nery Catalysts Are a Fluid Business " and " Making Cat Crackers Work on a Varied Diet; " be described in two pieces of articles, they publish in " Chemical Week " 1978.7.26 and 1978.9.13 on two phases respectively.The content that above-mentioned article is published also is hereby incorporated by.Usually, the zeolite that contains in the catalyzer of zeolite is those known components useful to the FCC process.These components generally are crystallization shape aluminosilicates, and its typical case constitutes, and to be four coordination aluminium atoms combine by Siliciumatom adjacent in Sauerstoffatom and the crystalline structure.Yet, " zeolite " this speech that uses among the present invention, not only be meant aluminosilicate, comprise that also those part or all of aluminium are other atoms (as gallium, phosphorus and other atoms metal) institute's metathetical material, and comprise that also all or part of silicon is by such as germanium institute metathetical material.With titanium and zirconium displacement also is feasible.
Most of synthetic or natural zeolite all are the sodium types, and sodium cation combines with the electronegativity position in crystalline structure.When sodium cation is exposed under the hydrocarbon conversion condition, particularly under hot conditions, can make zeolite be tending towards losing activity, and its stability is reduced greatly.Therefore, during as catalyst component, can make it carry out ion-exchange at zeolite, this ion-exchange can be carried out before or after this zeolite is infiltrated mixture.Be suitable for replacing that the positively charged ion of sodium has ammonium (can decomposite hydrogen), hydrogen, rare earth metal, basic metal etc. in the zeolite crystal structure.Various suitable ion exchange methods and can be switched to the positively charged ion that goes in the zeolite crystal structure all are very familiar for the professional.
In the natural crystalline aluminosilicate zeolites, can directly use or be used for of the present inventionly having as the component in the catalyzer:
Faujusite (faujasite), mordenite (mordenite),
Clinoptilolite (clinoptilolite), chabazite (chabazite),
Euthalite (analcite), erionite (erionite) and levyne
(levynite), dachiardite (dachiardite), paulingite
(paulingite), noselite (noselite), ferrierite
(ferrierite), heulandite (heulandite), scolecite
(scolecite), stilbite (stilbite), harmotome
(harmotome), phillipsite (phillipsite), brusterite
(brewsterite), flarite, howlite (datolite),
Sarcolite (gmelinite), caumnite, white gold-plating stone (Leucite),
Oriental lapis (lazurite), wernerite (scapolite), mesolite
(mesolite), ptholite, nepheline (nephelite),
Matrolite, offretite (offretite) and sodalite (soda-lite).
In the crystalline aluminosilicate zeolites of synthetic, be used for of the present inventionly having as catalyzer or as the component of catalyzer:
X type zeolite (Zeolite x), United States Patent (USP) № 2882244; Y-type zeolite (Zeolite y), United States Patent (USP) № 3130007 and A type zeolite (Zeo-lite A), United States Patent (USP) № 2882243; And Type B zeolite (Zeo-lite B), United States Patent (USP) № 3008308; D type zeolite (Zeolite D),
Canadian Patent № 661981; E type zeolite (Zeolite E), Canadian Patent
№ 614495; F type zeolite (Zeolite F); United States Patent (USP)
№ 2996358; H type zeolite (Zeolite H), United States Patent (USP)
№ 3010789; J type zeolite (Zeolite J), United States Patent (USP)
№ 3001869; Zeolite L (Zeolite L), belgian patent
№ 575117; M type zeolite (Zeolite M), United States Patent (USP)
№ 2995A23; O type zeolite (Zeolite O), United States Patent (USP)
№ 3140252; Q type zeolite (Zeolite Q), United States Patent (USP)
№ 2991151; S type zeolite (Zeolite S), United States Patent (USP)
№ 3054657; T type zeolite (Zeolite T), United States Patent (USP)
№ 2950952; W-type zeolite (Zeolite W), United States Patent (USP)
№ 3012853; Z type zeolite (Zeolite Z) Canadian Patent
№ 614495; And Omega type zeolite (Zeolite Omega), Canadian Patent № 817915.ZK-4HF, α, β zeolite and ZSM-type zeolite all are available.In addition, United States Patent (USP) № 3140249,3140253,3944482 and 4137151 described zeolites also are effective.The disclosed content of these patents also is hereby incorporated by.
Being applicable to of the present invention is the crystalline aluminosilicate zeolites with faujusite type crystal structure, particularly natural faujusite, X type zeolite and y type zeolite.
The industrial catalyzer that contains zeolite is carrier-containing, and these carriers are various metal oxides and composition thereof.They comprise: silicon-dioxide, and aluminum oxide, magnesium oxide and their mixture and the mixture of these oxide compounds and carclazyte one class, this is described in United States Patent (USP) № 3034948.For example people can select for use any to be applicable to the fluid cracking catalyst that contains zeolite molecular sieve of producing gasoline from decompression gas oil.But suitably select catalyzer for use, can obtain some advantage with anti-metallicity.For example a kind of zeolite catalyst with anti-metallicity of describing in United States Patent (USP) № 3944482 wherein contains 1-40%(weight) by rare earth metathetical zeolite, remaining is the refractory metal oxide with particular bore volume and size distribution.
In general, use size range about 5 to about 160 microns catalyzer for well, size range be about 30 to about 120 microns better.
Also can contain one or more combustion improvers in the component of catalyzer, it is favourable to the regeneration of next step catalyzer.During the Residual oil cracking, it is burnt to produce many depositions on catalyzer, and this burnt meeting reduces activity of such catalysts.In order to recover activity of such catalysts, the incipient scorch that generates is fallen in the regeneration stage.Regeneration is to make Jiao be transformed into the flue gas of carbon monoxide and/or carbonic acid gas.Known have a multiple material, when being sneaked in the cracking catalyst on a small quantity, just has to promote the burnt effect that is transformed into carbonic acid gas.This promotor can be selected for use in the type that can promote carbon burning again under condition or can optionally be made the Co type completely of can burning, its common consumption from trace to accounting for 10% or 20% of catalyst weight.
According to the present invention, formed logistics is to comprise hydrocarbon raw material, and catalyzer and low coking property solid particulate are at interior suspended substance.This suspended substance is upwards flowed, just can realize required hydrocarbon conversion reactions.The thinner material as steam or light gaseous hydrocarbons, also can be introduced the reactor riser bottom, so that raw material is gasified to greatest extent.
The equipment that process of the present invention is used, for quick gasification raw material as much as possible and be mixed feedstocks of hydrocarbons more effectively, catalyzer and low coking property solid particulate have been created condition, thereby the mixture that forms can be dilute suspension and flow with the flow pattern that increases progressively.The predetermined residence time at the end, catalyzer and low coking property solid particulate are told from hydro carbons, preferably make all or most of at least hydrocarbon and catalyzer and low coking property solid particulate sharp separation.This sepn process can be selected any short-cut method for use, comprises that the method for cyclonic separation method and so on realizes.Suspended substance mentioned above is transported to reactor riser, and this pipe unit is long narrow shape, and its length and diameter are 10 better than generally being at least about, and about 20 to 25 or better greater than 25.Reactor riser can be that the whole straight tubular of the equal pearl of diameter or diameter are along the cone barrel that reactor riser enlarges continuously or staged increases, so that fixing or change the flow velocity of material in the whole riser tube.Usually, the structural requirement of reactor has high relatively flow velocity, and wherein the aerosol density of catalyzer and low coking property solid particulate is low.For example the mean flow rate in the reactor riser is greater than about 25 feet per seconds (7.62 meter per second) usually, more typically is greater than about 35 feet per seconds (10.7 meter per second).This flow velocity can be up to about 55(16.8 meter per second) to about 75 feet per seconds (22.9 meter per second) or higher.This circulating capacity of riser tube will be enough to usually to prevent that catalyzer from piling up, thereby the catalytic amount that joins in the riser tube can be maintained less than about 4 or 5 pounds/foot at the bottom of bed or at other position of riser tube 3(64.1 or 80.1 kilograms/meter 3) level.Correspondingly the lifting capacity at upper reaches end of riser tube (i.e. bottom) and dirty end (being the top) two places is approximately less than 2 pounds/foot 3(32 kilograms/meter 3).
The flow pattern that increases progressively is related to catalyzer, raw material, and fluidic such as low coking property solid and product flow, by the conversion zone control fluidic forward flow of elongated nature and the direction that is maintained fixed.But this is not to possess strict laminar flow.Though once the someone thought, limit " landing " and back-mixing is feasible with enough low catalyst loading, but well-known, catalyzer and low coking property solid turbulent flow and " landing ", in the scope of a certain specific gas speed and a certain catalyst loading, may take place in various degree.Preferably reactor want can be on its riser tube one or more, make all gasiform cracked product most of with catalyzer and low coking property solid sharp separation.All gaseous state cracked product preferably will originally be separated with low coking property solid-based with catalyzer at the dirty end (top) of riser tube.
Preferable operational condition to method of the present invention is described as follows: in this law, preferably control the preheating of raw material, make raw material can absorb a large amount of heat from catalyzer and low coking solid, thereby the material temperature is brought up to invert point, the least possible use external fuel comes heating raw simultaneously.Therefore, as long as the Material Characteristics permission can at room temperature be fed in raw material.For the high raw material of carbon content, can be preheating to about 600 (316 ℃) left and right sides chargings, typical preheating temperature is about 200 °F (93.3 ℃) to about 500 °F (260 ℃), but does not get rid of higher preheating temperature.Catalyzer and low coking property solid particulate enter the temperature range of reactor riser can be very wide.For example, better from about 1200 ° to about 1600 °F (649 ° to 871 ℃) generally from about 1100 ° to about 1700 °F (593 ° to 927 ℃).
Hydrocarbon raw material changes into low-molecular-weight product, generally can carry out (temperature is measured at reactor outlet) under the temperature of about 850 ° to about 1400 (454 ° to 760 ℃).In the riser tube of reactor, all chargings can be gasified or not gasify, and this will be decided by selected feeding temperature and raw material properties.
Though the pressure in the reactor generally can be at about 10 to about 70 pounds/inch 2Change in (68.9 to 482.6 thousand handkerchief) scope, but be preferably in about 15 to about 55 pounds/inch 2In the scope of (103.4 to 379.2 thousand handkerchief).Raw material and the gaseous product residence time in reactor riser, generally can change between about 0.5 to about 6 seconds.Type and quantity, temperature and the pressure etc. of the length of the residence time and raw material, catalyzer and low coking property solid particulate all have relation.Professional in the hydrocarbon processing industry can select a suitable residence time easily for use, thereby obtain the benefit that the present invention can provide.Preferably to remain on weight ratio be about 1 in about 30 scope to the ratio of catalyzer and stock oil, and low coke solid particle arrives in about 10: 1 scope at about 1: 100 the weight ratio of cracking catalyst.
In general, the conditions such as ratio, temperature, pressure and the residence time of the ratio of catalyzer and stock oil, low coking property solid particulate and stock oil comprehensively, should select to such an extent that make remaining hydrocarbon material reach basic conversion.Per pass conversion is high to be an advantage of this law, and for example, transformation efficiency can surpass 60%, reaches about 90% or higher.Above-mentioned integrated condition maintains is enough to obtain about 60 to about 90% transformation efficiency just better, can maintain that to obtain about 65 to about 85% transformation efficiency then better.The algorithm of above-mentioned transformation efficiency is: the percentage ratio that is equal to or higher than the liquid product volume gained of 430 (221.1 ℃) with 100% volume that deducts the fresh liquid raw material divided by its boiling point.This high conversion may and be bound to produce sizable coking rate usually, for example, is that benchmark is about 3.5 to about 20% in the weight of raw material.
This process preferably includes decaying catalyst and low coking property solid particulate is separated later elution in gaseous product.The professional is familiar with the suitable scrub solution and the condition of elution decaying catalyst.
According to the present invention, when hydrocarbon-type oil being changed into light oil products, can produce sizable Jiao of quantity with high conversion, coke laydown needs careful on catalyzer and low coking property solid particulate during regeneration.In order to make catalyzer keep enough activity, need regenerate under certain condition.Conditions such as the time of catalyst regeneration, temperature and atmosphere will be enough to make the carbon content on the catalyzer to drop to about 0.25%(weight) or 0.25% below.Therefore, when handling residual oil, Jiao's amount that must burn in the breeding blanket is sizable.Some Jiao can be deposited on the low coking property solid particulate inevitably, thereby in RS Regenerator Section, on low coking property solid particulate, burn this part burnt process and also be counted as regenerative process, although this combustion processes substantial regeneration that is not catalyst activity.When using burnt this term to illustrate when of the present invention, should be understood to comprise that all that be deposited in after the elution on catalyzer and the low coking property solid particulate not have the hydrocarbon that gasifies.In the feedstock conversion, making catalyzer and low coking property solid renovation process is under the temperature condition of about 1100 to about 1600 (593.3 to 871.1 ℃), and the incipient scorch that deposits on it is fallen.In order to guarantee perfect combustion burnt in the revivifier,, can be recycled to the inlet of revivifier repeatedly from the thermocatalyst stream that revivifier comes out.
The burnt burning of deposition liberated heat is absorbed by catalyzer and low coking property solid particulate in the revivifier, thus this heat the regenerated solid mixture with very easily be retained before fresh feed contacts.In one embodiment of the invention, when handle hydrocarbon residual oil reached required transform level, the revivifier internal combustion produced a large amount of heat.The heat that reactor needs comprises heating raw and makes the required heat of the cracking reaction of heat, supply heat absorption of material gasification and the heat of post-reactor thermosteresis.The heat that revivifier produces is transported to reactor by the circulation of low coking property solid particulate and catalyzer.Thereby be possible by the temperature that the ratio that change is circulated in low coking property solid between revivifier and the reactor and catalyzer is controlled revivifier.This just provides a kind of by regulating low coking property solid particulate amount in low coking property solid of round-robin and the mixture of catalysts, independently controls the method for temperature of revivifier.
Now embodiment of the present invention will be described, and description of drawings is as follows: hydrocarbon raw material enters riser tube 2 through conduit 1, and contacts with the mixture of the regenerated catalyst of coming in by pipeline 13 with low coking property solid particulate.The mixture that hydro carbons, catalyzer and low coking property solid particulate form, above stream mode is passed riser tube 2 usually, and most of there hydro carbons generation conversion reaction enters reactor 4 then, and this reactor has an inner separated space 3 as the disengaging zone.Catalyzer separates with gaseous hydrocarbons there with low coking property solid particulate.The catalyzer of inactivation and low coking property solid particulate are collected in the bottom of reactor 4, with after conduit 7 discharge.The pressure reduction that records according to pressure transmitter 18 and 19 is by the flow velocity in charge level sensing, record and the controlling organization 20 control conduits 7.The variation of solid particulate material stock amount can be reflected in the variation of pressure reduction in the reactor 4.Controlling organization 20 keeps predetermined particle material stock amount by control valve 21.Be entrained with catalyzer and the fine grain gaseous hydrocarbons of low coking property solid, by cyclonic separator 5, reduced wherein solid content after, discharge from reactor 4 through pipeline 6.The solid particulate of separating has been got back to inner separated space from the lower end of cyclonic separator.As everyone knows, in fluid cracking technology, can use many cyclonic separators, and these cyclonic separators can be multistage, enter the second stage from first step cyclonic separator expellant gas.
Decaying catalyst by pipeline 7 contacts with the regeneration air of coming in through pipeline 8 (or oxygen) with low coking property solid particulate.The mixture of air, decaying catalyst and low coking property solid particulate imports through pipeline 8 between an inner separate chamber 9 revivifier 10.In revivifier, airborne oxygen and coking in conjunction with producing flue gas, obtain not containing relatively burnt catalyzer and low coking property solid particulate.The regenerated catalyst of gained and low coking property solid particulate are collected in the middle part of revivifier 10, discharge through pipeline 13 again, import reactor riser 2 as previously mentioned.Control valve 14 is installed on the pipeline 13, control the flow of regenerated catalyst and low coking property solid particulate according to the temperature of measuring, and controlling organization 15 receives and send corresponding signal by device 16 and 17.Shown in the figure,, near cyclonic separator 5 places a temperature sensing device 16 is installed, but also can selects other suitable temp that can reflect reactor 4, come direct control valve 14 on the top of reactor 4.Flue gas is discharged from revivifier 10 through gas-catalyst separation device 11 and conduit 12.
Following explanation is in order to make the professional can understand working method of the present invention more fully, so that therefrom obtain maximum value.
When low coking property solid particulate circulation time between the RS Regenerator Section conversion zone of known its specific heat and its coking tendency, following equation (1) can be used for estimating the RS Regenerator Section of fluidized catalytic cracker (FCC) or the temperature of revivifier.
(1) regenerator temperature after the balance=(A) (B) (C)+the T reactor
All independent operation parameters of supposing FCC apparatus all are maintained fixed, and when the coking property solid particulate is hanged down in adding in the round-robin catalyst charge, just can predict regenerator temperature with above-listed formula.The independent operation parameter comprises feeding temperature, feed composition, temperature of reactor, carbon monoxide pressure and the catalyst type at RS Regenerator Section incendiary degree, device.For the ease of calculating, during the operation FCC apparatus, what unique permission changed is the amount that joins the low coking property solid particulate in the recycling catalyst charging.
By fixing all independent operation parameters, can find out more significantly that low coking property solid particulate is to reducing the RS Regenerator Section Temperature Influence.Certainly, in industrial practice, in case the temperature of breeding blanket drops to required temperature boundary line, independent operation parameter above-mentioned can be adjusted usually thereupon, so that obtain the benefit that reduces the RS Regenerator Section temperature.
The factors such as coking tendency of the specific heat of the amount of the regenerator temperature after the balance and low coking property solid particulate and specific heat, FCC catalyzer, the temperature that adds revivifier before the low coking property solid particulate and low coking property solid particulate and FCC catalyzer are relevant.
In the superincumbent equation (1):
A=(Cp catalyzer)/(Cp catalyzer (1-C L C M S)+C P L C M S(C L C M S))
B=(T The revivifier initial temperature-T Reactor)
C=(D catalyzer (1-C L C M S)+D L C M S(C L C M S))/(D catalyzer)
In the formula: C LCMSAfter having added low coking property solid particulate, the weight fraction of this solid particulate in round-robin FCC catalyst charge;
C PCatalyzer is the specific heat of catalyzer;
C PLCMSSpecific heat for low coking property solid particulate;
T The revivifier initial temperatureFor adding the temperature of FCC revivifier before the low coking property solid particulate;
T ReactorBe FCC reactor concentrated phase temperature;
D CatalyzerBe " carbon is poor " on the catalyzer (percentage ratio of coking deducts surplus burnt percentage ratio on the FCC granules of catalyst after the regeneration on the FCC granules of catalyst of inactivation);
D LCMSBe " carbon is poor " on the low coking property solid particulate (weight percentage of coking on the low coking property solid particulate of discharging from reactor deducts the surplus burnt weight percentage of the low coking property solid particulate of discharging from revivifier).
Analysis revealed to " A " above-mentioned: the low coking property solid particulate with high specific heat should be more effective, falls required should low coking property solid amount less because make revivifier reach given temperature.But should point out that even the specific heat of low coking property solid particulate is low, it is feasible that this process remains, but will be with more low coking property solid particulate in order to reach same effect.
" C " above-mentioned item shows, " carbon is poor " of low coking property solid particulate low or " carbon is poor " be zero optimum, because the additional coking that low coking property solid particulate produces causes heat release extra in the FCC revivifier, can make the effort of attempting to reduce regenerator temperature be cancelled or be suppressed.
Because it is fixed that the heat that the FCC reactor needs is actually weighing apparatus, and FCC apparatus is under the fixed operational condition of weighing apparatus, under thermal equilibrium state, move,, all can play and the previous identical consequence that on round-robin FCC catalyzer, produces the coking effect as long as on low coking property solid particulate, burnt deposition is arranged.Therefore, coke laydown can reduce the granules of catalyst amount that is transported to every pound of raw material that riser tube goes on low coking property solid particulate, promptly reduce the ratio of catalytic amount to the raw material oil mass, thereby can find that transformation efficiency reduces in the FCC reactor.This impels people to select the solid particulate of few coking or noncoking for use, makes its disadvantageous effect to the operation of FCC reactor reach minimum degree.
The following examples are the explanations to preferable embodiment of the present invention, are not to be used for being limited to the overall range of the present invention that proposes in the appended right item.
Example one
Advantage is in order to demonstrate the invention tested in plant-scale fluidized catalytic cracking chemical plant.These tests all are to be benchmark with the mixture that splits be situated between decompression gas oil and long residuum.Decompression gas oil and long residuum are all obtained from a kind of domestic heavy oil, and this content that mixes long residuum in the oil plant is the 8.4%(liquid volume percent).Listed the analytical results of these feed oil components in the table one.
Table one charge raw material oil analysis
Decompression gas oil long residuum
Severe, degree Beaume (kilogram/rice 3) 25.8(899) 16.5(955)
Sulphur content, weight percentage 0.93% 1.49%
Carbon residue, weight percentage 0.29 8.5
Nickel+vanadium (hundred is several very much) 0.2 34
Distillation
Initial boiling point (℃) 540(282) 675(357)
5% 635（335） 800（426）
20% 690（365） 890（476）
40% 752（400） 980（526）
60% 835（446） 1065（573）57%
80% 932（499）
95% 1040（559）
Final boiling point (℃) 1076(580)
Rate of recovery % 99 57
Tower bottoms productive rate % 1 43
These tests are to be to carry out in the riser reactor that makes progress of the cocurrent flow of fluid cracking catalyst with the zeolite at one.The operational condition of these two tests: the pressure of reactor is 18Psig pound/inch 2Gauge pressure (1,124 thousand handkerchiefs/gauge pressure).First test of being done has been represented the situation of the charge raw material oil that contains long residuum being carried out processing treatment with common fluid catalytic cracking (FCC) reactor as a benchmark.The operational condition of first test is: catalyzer is 6.7 with the feed oil ratio, the feed oil temperature is 441 °F (227 ℃), temperature of reactor is 972 °F (521 ℃), the regenerator temperature of gained is 1368 °F (774 ℃), fresh feed oil transformation efficiency is the 81.7%(liquid volume percent), wherein produce gasoline be about the 62.5%(liquid volume percent), research octane number (RON) is 92.7, coke yield is the 5.6%(weight percentage).
The test of the carrying out second time is intended for comparison, is the example of one embodiment of the invention.The charge raw material oil that contains long residuum of testing for the second time usefulness is identical with the stock oil of testing for the first time usefulness.The operational condition of test is for the second time: the catalyst/oil ratio is 6.5, and the feed oil temperature is 475 °F (246 ℃), and temperature of reactor is 970 °F (520 ℃).This test contains the inorganic oxide particles that hangs down coking in being circulated in the catalyzer of reactor, its quantity is about 1/9 of catalyst weight, or catalyzer is 9: 1 with low coking solid ratio.Low coking inorganic oxide solid particulate used in this test is α-Al 2O 3, its specific surface area is less than 1 meter 2When/gram is checked with the ASTM-MAT method, at these useless α-Al 2O 3Top knot charcoal percentage ratio is zero, and therefore the ratio of resulting solid (catalyzer adds low coke solid particle) and feed oil is 7.5.And the temperature of finding revivifier only is 1337 °F (725 ℃), and is lower than the regenerator temperature 1368 (742 ℃) of test for the first time.The transformation efficiency of charging is the 80.5%(liquid volume percent), and its gasoline yield is the 62.7%(liquid volume percent).Research octane number (RON) is 92.5, and coke yield is the 5.6%(weight percentage).Should be noted that feeding temperature is 475 °F (246 ℃) in second test, and the feeding temperature in first test is 441 °F (227 ℃), promptly well-known than low 34 °F (18.9 ℃) in second test, for this class fluid catalytic cracking operation, the increase of feeding temperature will cause the increase of regenerator temperature.Therefore, reduce if will have greatly with the temperature of lower temperature charging revivifier in second test.In order to be easy to comparison, the result of these two tests is shown in the table 2:
Table two test brief summary
Operational condition:
(FCC) catalyzer/low knot that project is common
Burnt solid
Catalyzer/low coking solid, mass ratio 10,0/0 90/10
Feeding temperature, °F (℃) 441(277) 475(246)
Reactor pressure, (thousand handkerchief gauge pressure) 18(124) 18(124)
Temperature of reactor, °F (℃) 972(521) 970(520)
The catalyst/oil ratio, kg/kg 6.7 6.7
Total solids/oil ratio, kg/kg 6.7 7.5
Catalyzer/low burnt solid ratio, kg/kg-9
Regenerator temperature, °F (℃) 1368(742) 1337(725)
Products distribution
C 2Weight % 4.1 4.0
C 3Liquid volume % 12.7 12.2
C 4Liquid volume % 15.6 14.8
Gasoline, liquid volume % 62.5 62.7
Solar oil, liquid volume % 11.1 12.4
Clarifying slurry oil, liquid volume % 7.2 7.1
Produce burnt rate, weight percentage % 5.6 5.6
Overall yield, liquid volume percent % 109.1 109.2
Transformation efficiency, liquid volume percent % 81.7 80.5
Gasoline research method octane value 92.7 92.5
The above solid particulate of low coking that comparison shows that uses the quantity of the coke of generation to use the coke quantity that catalyzer produced identical with independent with cracking catalyst together.Transformation efficiency is identical substantially with the product productive rate for these two tests.Viewpoint from operation, the shown special advantage of test of adding the solid particulate of low coking in the catalyzer is that it can make catalyst regenerator operate down at 1337 °F (725 ℃), that is the FCC process low 31 °F (172 ℃) more common than base case.
As above mentioned, lower regenerator temperature helps to keep the cracking activity of catalyzer, the selection for operational condition simultaneously also provides greater flexibility, may eliminate or can reduce the requirement that the exterior cooling of catalyst regenerator facility is provided at least.The temperature of revivifier can be controlled the method for the ratio of it and mixture of catalysts independently with the solid of the low coking of change.
Example two
But this example mainly is the result who demonstrates the test of various fluidizing solid particulates.In test, these solid particulates can be thought with the solid particulate that accords with ASTM-MAT method inspecting standard mentioned above basic identical.The used feed oil of test in this example is the heart cut gas oil by Sino-U.S. state (Mid-Continent) heavy oil extraction.The character of this heart cut gas oil is listed in table three.
The character of table three, Sino-U.S.'s state gas oil
Severe, 60 (kilogram/rice of degree Beaume 3) 31.8(866)
Sulphur content, weight % 0.26
Nitrogen content, weight % 0.03
Heavy metal, (1,000,000/, PPM) 3
Distillation
Initial boiling point (℃) 458(236)
20% 581（305）
50% 660（349）
70% 703（373）
95% 775（413）
Do °F (℃) 810(432)
Above gas oil described in the table 3 be feed oil used in this example, desired ASTM standard feed oil phase is similar in it and the ASTM standard process, but and incomplete same.We attempt removing to replace ASTM standard feed oil with it.
This test is partly formed by two: add the particle sample of 4 grammes per square metres in the reactor (1), and (2) spray into reactor to above-mentioned feedstock diesel with the input speed that restrains for 75 seconds 1.3, and the temperature maintenance of reactor is at 900 °F (482 ℃).The weight ratio of particle and oil is about 3 in the experiment, and per hour space velocity is about 15.4.
γ-Al 2O 3Particle (sample) sample, γ-Al 2O 3Particle and incinerating kaolin particle are tested in above-mentioned test respectively.The result of the characteristic of these three kinds of materials and test respectively is illustrated in the table.
Table four, test-results
On the useless solid of specific surface area (BET) hole volume transformation efficiency
Rice 2/ gram centimeter 3Jiao of/gram volume % face knot
Charcoal weight %
γ-Al 2O 3＜1 0 4.1 0
γ-Al 2O 3205 0.92 7.3 0.32
Calcined kaolin (3 hours 9 0.0154 6.6 0.08
1600°F（871.1℃）〕
γ-the Al of test usefulness 2O 3Be that specific surface area is 30～1000 meters 2/ gram, the hole volume is 0.05～2.5 centimetre 3The representative aluminum oxide of/gram is used as the thinner of catalyst for cracking in Olympic Competition row people's such as (Occlli) English Patent (NO2116062).Data in the table four show, γ-Al 2O 3Have the 7.3%(volume) transformation efficiency and 0.32%(weight arranged) coke buildup at exhausted γ-Al 2O 3On the particle, this particulate specific surface area is 205 meters 2/ gram.According to the present invention, the solid particulate that selected conduct has a low coking property is with the check of ASTM-MAT method the time, and the carbon that generates at useless particle surface must be less than about 0.2%(weight).This particulate specific surface area is less than about 5 meters 2/ gram does not have substantial effect to the operation of conversion zone.Because γ-Al 2O 3On accumulated a considerable amount of coke and the tendency that transforms hydrocarbons arranged, so the operation of the conversion zone of FCC process is had a negative impact, so γ-Al 2O 3It is not the low coke solid particle of a kind of satisfaction among the present invention.
It is believed that the used burnt kaolin of test mentioned above is a kind of representational calcined kaolin.At United States Patent (USP) NO.4289605(Bartholic) in, this kaolin is considered to a kind of macroporous inert substance that has, and it is added in the active catalyst and goes.By the data in the table four as can be seen, burnt kaolin has the 6.6%(volume) transformation efficiency, on useless kaolin particle, accumulated 0.08%(weight) coke, specific surface area is 9 meters 2/ gram.According to the present invention, alternative low coking property particle must possess following parameter: with the check of ASTM-MAT method the time, must be less than about 0.2%(weight in the coking amount of useless particle surface); Its specific surface must be less than about 5 meters 2/ gram; It is to the operation of the conversion zone substantial influence that do not have.And burnt kaolin had both accumulated a certain amount of coke, had the tendency that changes hydro carbons again, can also produce adverse influence to the operation of the conversion zone of FCC apparatus.Simultaneously, its surface-area is greater than 9 meters 2/ gram.Therefore, as test-results, burnt kaolin is not suitable as low coking property solid particulate required for the present invention.
According to the present invention, easy fluidizing α-Al 2O 3Particle is only so-called low coking property particle.Data in the table four show, α-Al 2O 2Have minimum transformation efficiency: the 4.1%(volume), during with the check of ASTM-MAT method at useless α-Al 2O 3Do not have to detect the coke of output on the particle, specific surface area is less than 1 meter 2/ gram.In order to obtain maximum benefit from method of the present invention, but the low coking particulate specific surface area of this kind fluidizing is preferably less than about 5 meters 2/ gram is with the check of ASTM-MAT method the time, at useless γ-Al 2O 3The amount of coke that generates on the particle surface is less than about 0.2%(weight).When checking with the ASTM-MAT method, the amount of coke that generates on useless low coke solid particle is more more suitable than 0.2% much smaller the sort of easy fluidizing low coke solid particle.The particle of only low coking property, its surface-area is less than about 5 meters 2/ gram.With the check of ASTM-MAT method the time, the coking amount on useless low coking property solid particulate is less than about 0.05%(weight).
Must be pointed out that it is inevitable that the easy fluidizing solid particulate that adds for the purpose of controlled temperature forms coking in its surface.This is the non-selection cracked cause owing to stock oil, at this moment because the product structure that obtains in the reactor has very big disadvantageous effect.Nature, the detrimental action of the auxiliary material of this solid increases along with the increase of the amount of coke that generates, and therefore, no matter is for the suitable operation of reactor or in order to reach the temperature that reduces revivifier, low coking property is a very basic characteristic.
Figure 86100906_IMG1

Claims (9)

1, the method for a fluidized catalytic cracker of operation, this device comprises a RS Regenerator Section and a conversion zone, when [recovered temperature of its 50% (volume) cut is higher than 500 °F (260 ℃)], its working method comprises at the high carbon residue hydrocarbons raw oil of processing:
(a) under the condition that heat absorption, coking change, but make above-mentioned raw materials oil after conversion zone and fluidizing, regeneration the thermally splitting catalyzer and the mixture with on-catalytic solid particulate that contains resistant to elevated temperatures inorganic oxide of low coking property contact, the ratio of low coking property solid particulate and cracking catalyst is about 1: 100 to about 10: 1 in this solid mixture, and the specific surface area of low coking property solid particulate is less than about 5 meters 2/ gram, its coking ability is less than about 0.2% (weight) with the check of ASTM-MAT method the time;
(b) the hydrocarbon product that generates with tied burnt catalyzer and low coking property solid particulate is separated,
(c) reclaim hydrocarbon product,
(d) cracking catalyst and low coking property solid particulate are sent to above-mentioned RS Regenerator Section, next with the heat release burning of the coke on the solid its heating and regeneration,
(e) contact with stock oil by described in the above-mentioned steps (a) cracking catalyst after the heating of gained and the regeneration and low coking property solid particulate being delivered to conversion zone from RS Regenerator Section, compare with the same operation of not adding low coking property solid particulate, this method can make RS Regenerator Section maintain on the lower temperature, and the while is not reduced the carbon-burning capacity of RS Regenerator Section, does not influence the operation of conversion zone yet.
2, in the described method of claim 1, comprise α-Al in the wherein low coking property solid particulate 2O 3
3, in the described method of claim 1, wherein the specific surface area of low coke solid particle is less than about 5 meters 2/ gram, with the check of ASTM-MAT method the time, the coking ability on useless low coke solid particle is less than about 0.05%(weight).
4, the described method of claim 1, wherein the overall size range of low coking property solid particulate is about 5 to about 2000 microns.
5, the described method of claim 1, wherein catalyzer and the low coke solid particle after the regeneration is to be added to conversion zone under about 1200 °F to about 1600 °F (649 to 871 ℃) in temperature range.
6, the described method of claim 1, wherein the conversion condition of conversion zone comprise pressure by about 15 to about 55 pounds/inch 2(103～379,000 handkerchief), the weight ratio of catalyzer and stock oil are about 1: 1 to being about 30: 1, and temperature range is about 850 to about 1400 °F (454～760 ℃).
7, handling a kind of its 50%(volume) the fluid catalytic cracking process of fraction temperature greater than the high carboloy residue hydrocarbons raw oil of about 500 (260 ℃) in, make stock oil under the cracking conditions of heat absorption and the granulous solid cracking catalyst that was heated of round-robin contact at conversion zone, each component in the stock oil is converted into more lower boiling hydro carbons, cocurrent flow cooling and the deposition of carbon on catalyzer along with catalyzer, the carbonaceous pollutent loses activity catalyzer, be used in the method for RS Regenerator Section burning-off carbonaceous sediment, the catalyst regeneration that can make contaminated and regain catalysis split be situated between active, under the heat release condition, may make the temperature of catalyzer and RS Regenerator Section reach a unacceptable or nonconforming maximum temperature, and after this will be such heating, the regenerated catalyzer is sent to conversion zone by RS Regenerator Section, but improvements of the present invention are to mix the into solid particulate of the low coking of fluidisation in the circulation of cracking catalyst, just can be reduced in the top temperature that RS Regenerator Section can reach, and this low coke solid particle of the amount of burnt that does not reduce RS Regenerator Section mainly comprises resistant to elevated temperatures inorganic oxide, and its surface-area is less than about 5 meters 2/ gram, its coking ability is lower than about 0.2%(weight when checking with the ASTM-MAT method), the amount of these solid particulates that add must satisfy that to make they and the ratio of cracking catalyst be from about 1: 100 to about 10: 1, and the RS Regenerator Section temperature that just can reduce like this is from about 10 °F to about 250 °F (6～139 ℃) and the while does not influence the operation of reactor.
8, improving one's methods that claim 7 requires, wherein the low coke solid particle that is added mainly comprises α-Al 2O 3
What 9, require in claim 7 improves one's methods, and wherein the specific surface of the solid particulate of low coking is less than about 5 meters 2/ gram, during with the check of ASTM-MAT method, its coking ability is less than about 0.05%(weight).
CN86100906.1A 1985-02-20 1986-02-01 Reducing the temp. in a regeneration zone of a fluid catalystic cracking process Expired CN1004141B (en)

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CN110950729A (en) * 2018-09-27 2020-04-03 中石化洛阳工程有限公司 Method and equipment for improving selectivity of low-carbon olefin

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CA1154735A (en) * 1978-09-11 1983-10-04 Stanley M. Brown Catalytic cracking with reduced emissions of sulfur oxides
US4311581A (en) * 1980-01-07 1982-01-19 Union Oil Company Of California Process for reducing CO and SOx emissions from catalytic cracking units
AU557769B2 (en) * 1981-09-14 1987-01-08 W.R. Grace & Co.-Conn. Catalytic cracking of sulphur-bearing hydrocarbon feedstocks and spinel component catalyst
GB2114146A (en) * 1982-01-29 1983-08-17 Engelhard Corp Preparation of FCC charge by selective vaporization
AU555438B2 (en) * 1984-01-04 1986-09-25 Mobil Oil Corp. Fcc process
US4608357A (en) * 1984-02-06 1986-08-26 Engelhard Corporation Catalytic cracking with mullite composition promoted combustion of carbon monoxide

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CN110950729A (en) * 2018-09-27 2020-04-03 中石化洛阳工程有限公司 Method and equipment for improving selectivity of low-carbon olefin
CN110950729B (en) * 2018-09-27 2022-06-07 中石化洛阳工程有限公司 Method and equipment for improving selectivity of low-carbon olefin

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